Dyestuffs of the anthraquinoneacridone series



Patented June 1 18 1935 genanthraquinone 2,1 (N) .1 s obtained therewithr which dyeings exhibit good thealiphatic and hydroaromatic series. 16

' fastness pr p rti s-1 I :iThe" said 4-.acylamino-Bz2,3,5-trihalogenan- The 4-amino-Bz2,3,5-trihalogenanthraquinone thraquinone-2,l fiNbbenzacridones may, however, 2,1(N)-benzacridones are be'stiprepare'dby heatalso be produced by synthetic methods,'viz.'by ing Bz2,3,5 trihalogenanthraquin'one- 2,1 (N) condensing l acylamino-l-halogenanthraquin- 5 benzacridones with strong'nitric acid; preferably. ones with, 2,3,5-trihalogen 6-aminobenzener1- 1'5 in an inert organic solvent, such'jas nitrobenzene, carboxylicacid orran ester thereof; orxeacyla and reducing. the nitro compound thus obtained, amino-4-halogenanthraquinoner2-carboxylicacid for example by vatting or by means of sodium sulor ester thereof with l-amino-2Ag5-trichl0rphide. The 'Bz2,3,5-trihalogenanthraquinone benzene, and-'efiecting ring'closure to formthe g 2,1(N)-benzacridones used as initial material acridones from the said condensation products may be produced synthetically by condensation of according to known methods. 1-chloranthraquindne-2carboxylic acid or an The 4-acylamino- Bz2,3,5-trihalogenanthraester thereof with 1-amino=2,4,5-trihalogenbenquinone ZJ-(N) -benza,cridones which are f ob-; zene or l-chloranthraquinone with 2,3,5-trihalotai-ned:intheaforedescribed manner in very good gen-fi aminobenzene-l' carboxylic acid or anester yields and agstateof highpurity may, if necessary, 25 thereof, and efiecting ring closure to form the ,be-furtherpurified according'to known methods, acridone ring according to customary methods. torexamplaby extraction with inert'organic sol- The said trihalogenanthraquin0ne-2,1(N)-benz vents, by-recrystallization from suchsolvents, by acridones may also be prepared by treating anrevatting; or treating theirpastes withoxidizing 3Q thraquinone-glm) -benzacridoneor its Bz3,5-di= agents, for example, alkali metal hypochlorite 3 halogen derivatives withhalogen in' acid solution, solutions, or by way of their-sulphates. They dispreferably sulphuric-or; chlorsulphonic acid solusolve in concentrated sulphuric acid to give usution and in the presenceof a halogentransferrer. allyorangesolutions and dyecotton. violet to blue The acylation. of the 4-amino-Bz2,3,5 -trihaloto greengblueto green gray shades from violet:

genanthraquinone-2,1(N) -benzacridones is preftoviolet-bl-uevats. j I V 35 'erably efiected in an inert organic diluting me- 'Thef most valuabledyestufis are those contain- 1 dium, such as for example nitrobenzene, trichlo ins Chlorine-in -the-Bz2,3-,5-positions, but the -in+ robenzene, pyridine, quinoline, xylene, naphthavention also oomprisesthe corresponding bromo lene and the like, it ,may, however, also be carderivatives; and,'-such iniwh ch p Of Said; I

40 ried out in the absence=of such diluting media. po q s.- eu chlorine and pa t by- .40 Acid-binding agentsmay'also be added to the reb om ne. Y I k l action mixture, forexample', tertiary bases and T e'f w s mp i z u t e illustrate alkali metal salts of weak acids Acylating agents h at o the present invention h nv nr. I which may be used for the'purpose of the present tion isn'otrestricted-thereto. The parts are by invention are in particular the halides and an- 3 2Q005311 l I on QI YESTUFFSIIOF Tina ANTHRAQUINONEnQ- e RIDONE Max Albert Kunz, Mannheim,

and Karl Koeberle,

SERIES and Erich Berthold Ludwigshafen-on-the- Rhine,-Germany, assignors-td GeneralAniline Works, Ind, New York, N. 2., a corporation.

of Delawar No Drawing. Application:

March 31; 1932, 1Serial No. 602,402. In GermanyAprilZ, 193

7 Claims. (01.260537) x The present .invention relates to vat dyestuffs of the anthraquinoneacridone series and process of producing the same." I

We have found that 4-amino-Bz2,3,5-trihalobenzacridones and their acyl derivatives arevaluable vat dyestuffs since they have the property of equally dyeing viscose silk and cotton so that even dyeings on mixed fabrics from the said fibrousmaterial are hydrides of organic, in particular aromatic, acids, such as for example the halides and anhydrides of benzoic acid and its substitution products, for example? the alkyl-, alkoxy-," halogen, cyane and nitro substituted derivatives, further. the said deriva'tives of afandpmaphthoic acid," anthra I cenevand: anthraquinonejcarboxylic acids, thiazol':

carboxylic; .acids' or "of. dicarboxylicf acids of the benzene and naphthalene'series. Furthermore;

there may he usedthe. said derivatives of "(ii-- phenyl-,,;ybenzophenone-;i diphe'nyl ether monoand polycarboxylic acids. however, alsov becarried' out- The acylation may, with the halides and anhydride'siof mono-and poly carboxylic acids ofex mplar} 428 ,partsfjof"Bzlafi-trichloro-anthraquinone 2,1(N) .-"benzacridoneare slowly heated "while stirring to betweenlflfl? andFiCQin 4000'parts of manner.

nitrobenzene after the addition of 800 parts of 96 per cent nitric acid and kept at the said temperature for between 4 and 6 hours. After cooling, the reaction mixture is worked up in the usual The 4 nitro-Bz2,3,5-trichloroanthraquinone-2,1(N) -benzacridone obtained in a practically theoretical yield forms red compact crystals, dissolves in concentrated sulphuric acid to give an orange solution and dyes cotton from a violet vat green gray shades of very good fastness.

Instead of reducing the nitro compound by vatting it may also be reduced by means of sodium sulphide. The amine is a violet black powder.-

I Example 2 44 parts of -amino-Bz2,3,5-trichloroanthraquinone-2.1(N) -benzacridone are heated to boiling while stirring in 460 parts of nitrobenzene with 20 parts of benzoyl chloride until unchanged initial material cannot anymore be detected which may be recognized from the fact that a sample does not anymore yield blue gray, but pure blue dyeings.

solves-in. concentrated sulphuricacid to give an orange solution and dyes cotton from a blue violet vat clear blue shades of excellent fastness to chlorine, light and atmospheric influences and is particularly suitable for printing purposes.

. The 4 parachlorbenzoyl amino Bz2,3,5-trichloroanthraquinone-2,l (N) -benzacridone have similar properties, it yields,however, blue shades 35 having a slightly more reddish tinge. The aoylation by means of anthraquinone-2-carboxylic acid yields a reaction product dyeing gray blue shades of excellent fastness.

When using 4-amino-Bz2-bromo-Bz3,5-dichloroanthraquinone 2,1 (N) benzacridone (obtainable from the Bz2-brom'o-Bz3.5-dichloroanthra 'quinone-2,1(N)-benzacridone in the manner described in Example 1) as initial material instead of the corresponding trichloro derivatives a reaction product is obtained dyeing gray green shades. 7

The acylamine prepared from 4-amino-Bz2,3,5- trichloroanthraquinone-2,1 (N) -benzacridone and oxalyl chloride dyes cotton blue shades; the reaction products obtained by means of the chlorides of terephthalic-, isophthalic, diphenylcarboxylic, naphthoic, naphthalene-1,5-dicarboxylic and anthraquinonebenzacridone carboxylic acids dye cotton violet to blue to green blue shades.

Example 3 440 parts of 4-amino-Bz2,3,5-trichloroanthraquinone-2',1(N) -benzacridone are heated to boiling for a short time in 5000 parts of nitrobenzene with 400 parts of paramethoxybenzoyl chloride. After cooling, the reaction product is filtered off. The pure 4-paramethoxybenzoyl-amino-Bz2,3,5- trich1oroanthraquinone-2,1 (N) -benzacridone obtained inavery good yield dissolves in concentrated sulphuric acid to give an orange solution and dyes cotton from a violet blue vat blue very fast shades.

The corresponding paraethoxybenzoylamino derivative likewise dyes blue shades as does also the acylamine produced by means of meta-nitroparamethylbenzoyl chloride.

Violet shades are' obtained with the products obtained by means of 2,5-dichlorobenzoyl chloride and metachlorobenzoyl chloride.

Example 4 44 parts of 4-amino-B22,3,5-trichloroanthraquinone-2,1(N) -benzacridone are heated to boiling while stirring in 220 parts of acetic acid anhydride until unchanged initial material cannot anymore be detected and a sample dyes blue shades fast to chlorine. The reaction mixture is then allowed to cool and the separated product filtered off. It dissolves in concentrated sulphuric acid to give an orange solution and dyes cotton clear blue shades of good fastness properties from a violet vat.

Inan analogous manner the aoylation by means of succinyl chloride, malonyl chloride, propionyl chloride and other halides or anhydrides of aliphatic carboxylic acids may be carried out.

What we claim is: 1. Vat dyestuffs of the anthraquinoneacridone series corresponding to the formula Hal Hal The reaction mixture is thenallowed to cool and the reaction product separated in the" form of dark violet'crystals filtered-off. It disin which X stands for a hydrogen atom or OC-R, B being a radicle of the benzene series, which dyestufis. dissolve in concentrated sulphuric acid to give usually orange solutions and dye cotton violet to blue to green blue and green grey shades.

2. The vat dyestuff of the anthraquinoneacridone series corresponding to the formula:

Hal.

N-Hn dissolving in concentrated sulphuric acid to give an orange solution and dyeing cotton from a violet vat green gray shades.

3. Vat dyestufis of the anthraquinoneacridone series corresponding to the formula:

O il -O C-R in which'R stands for an aromatic radicle, which dyestuffs dissolve in concentrated sulphuric acid to give orange solutions and dye cotton violet to blue to green blue shades.

series corresponding to the formula:

10 H-N c1 20 in which R stands for a radicle of the benzene series, which dyestufis dissolve in concentrated sulphuric acid to give orange solutions and dye cotton violet to blue to green blue shades.

5. The vat dyestuff of v the anthraquinone- 0 dissolving in concentrated sulphuric acid to give an orange solution and'dyeing cotton from a blue violet vat blue shades.

6. Vat dyestuffs of the anthraquinoneacridone the formula:

. series corresponding to 4. Vat dyestuifs of the anthraquinoneacridone in which R stands for series substituted byan a radicle of the benzene alkoxy group, which dyestufis dissolve in concentrated sulphuric acid to give orange solutions and dye cotton from violet blue vats blue shades.

7.- The vat dyestuff of the anthraquin0neacridone series corresponding to the formula:

dissolving inconcentrated sulphuric acid to give an orange solution and dyeing cotton from a blue violet vat blue shades.

MAX ALBERT KUNZL ERICH BERTI-IOLD. KARL KOEBERLE.

so I 

